Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
  • C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
  • C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/6828—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
  • C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
  • C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/6928—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/92—Fire or heat protection feature
  • Y10S428/921—Fire or flameproofing
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31616—Next to polyester [e.g., alkyd]
  • Y10T428/3162—Cross-linked polyester [e.g., glycerol maleate-styrene, etc.]

Definitions

• fusible compositions in which phosphorus is chemically combined prior to the cross-linking reaction either in the unsaturated polyester or in the unsaturated cross-linking agent.
• compositions are chemically different from the products of this invention because the double bond remaining in the linear unsaturated polyester so produced is highly reactive and can enter directly into the cross-linking reaction, whereas, the corresponding linkage in the halogen-containing deriva 2,931,746 Patented Apr. 5, 1960 ice . 2 tives employed in making the compositions of this invention is non-reactive in said copolymerization reaction. Moreover, they do not possess flame retardance.
• a further object is to provide resinouscor'npositions which .are highly resistant to exposure at elevated temperatures.
• a still further object is to prepare resinous compositions which are suitable for casting, molding, foaming or laminating and which are characterized by possessing the desirable properties usually required in resins in the preparation of castings, moldings, foamed articles and laminates, and which are also characterized by being capable of forming articles of commerce which have a pleasing appearance and wide utility.
• a particular object of this invention is to make available in commerce compositions comprising a mixture of an unsaturated polyester and an olefinic cross-linking agent,
• a further objective is to provide methods for chemically combining hexahalocyclopentadienes in the form of an adduct into the polyester.
• a still further ob jective is to provide methods for the preparation of these unsaturated polyesters and their combination with olefinic cross-linking agents.
• the principal objective of this invention is to incorporate phosphorus chemically into a component of the polymerizable mixture of the aforementioned unsaturated polyesters, or by means-of the olefinic cross-linking agent so that the final copolymer contains phosphorus in chemical combination, thereby obtaining a final copolymer which possesses greatly improved resistance to fire over such resins without phosphorus, improved resistance to weathering over such non-containing phosphorus resins, and also possessing good -color characteristics among other advantages. 7
• the unsaturated polyester may contain the component which imparts flame retardance in either the polycarboxylic acid or anhydride unit and/or in the polyhydric alcohol unit of the polyester.
• the unsaturated polyester must contain unsaturation which is capable of copolymerization with the unsaturation in the cross-linking agent. Such copolymerizable unsaturation is an essential characteristic of the unsaturated polyester portion of the mixture of this invention.
• polyester chain which is derived from the reaction adducts of hexahalocyclopentadienes with monoolefinic polycarbo'xylic acids or anhydrides, or mono-olefinic polyhydric alcohols or, esters thereof including acid chlorides is not sufiiciently reactive to enter into the cross-linking reaction.
• polyesters copolymerizable in the cross-linking reaction by incorporating in the esterification product a reactive and unsaturated chemical ingredient which retains its active unsaturation after being chemically combined in the polyester chain.
• flame retardant components in the unsaturated polyester as just described, and
• the cross-linking agent may contain the component which imparts flame retardance to the polyester resins of this invention.
• the reactant components which impart flame retardance to the final polymerized resinous compositions in cluded in this invention, i.e., the polyester resins, may best be prepared by effecting the chemical addition of a hexahalocyclopentadiene with an unsaturated polycarboxylic acid or acid anhydride or acid halide, or an unsaturated polyhydric alcohol, or esters thereof, presumably in accordance with the following equations, respectively, in which the specific reactants are given for purposes of illustration only:
• a particularly suitable material for this use is maleic anhydride; however any unsaturated polycarboxylic acid or anhydride, or, polyhydric alcohol, or, esters thereof, including the acid chlorides, capable of esterification without losing its ability to copolymerize with olefinic cross-linking agents may be employed.
• compositions of this invention which have only moderate flame resistance, because of a lowered halogen content, have excellent flame resistance when chemically combined phosphorus is included in the composition.
• halogen content of the final copolymerized resins in the examples following is shown to be approximately between 21 and 29 percent, halogen percentages as low as 7 percent may be used by taking advantage of the fire resistant properties lent to the composition by the chemically combined phosphorus while still maintaining the good flame resistance of these resins.
• the upper limit of halogen content is dictated by the molar limit of halogenated intermediate that can be used in the polyester while still maintaining copolymerizable unsaturation in the polyester chain. This upper limit is in the neighborhood of 57 percent if the cross-linking agent is of the unhalogenated type and 59 percent when both the polyester and cross-linking agent are halogenated.
• halogen content of the polyesters is lowered, increasing amounts of phosphorus are added in order to maintain. go'od flame-resistance characteristics of the final polymerized resin.
• Relatively small percentages of phosphorus, based on the final copolymerized resin, are all that are required in order to preserve good flame resistance. These percentages normally will vary between approximately 0.1 percent and 2.5 percent although compositions employing as low as 0.05 percent are suflicient to show some improved flame resistance and quantities of phosphorus as high as approximately 10 percent may sometime be fully chemically incorporated depending upon the types of polyester, cross-linking agent and phosphorus introducing chemical employed.
• phosphorus containing materials which may be used in order to chemically combine the phosphorus in the'copolymerized resin by introducing the phosphorus as a part of the polyester portion of the resins of this invention are: phosphorus oxychloride, phosphorus pentachloride, hydroxymethyl phosphonic acid, phosphorous acid, phosphorus trichloride, phosphoric acid, benzene phosphonic acid, tris methylol phosphine oxide, bis-hydroxymethyl phosphinic acid and the like.
• phosphorus containing materials which may be used in order to chemically combine the phosphorus in the copolymerized resin by introducing it as a part of the monomeric cross-linker are diallyl benzene phosphonate, bis (betachloroethyl) vinyl phosphonate, di- (chloropropyl) propenyl phosphonate, tri-allyl phosphate, di-allyl ethyl phosphate, allyl diethyl phosphate, allyl propyl phosphate, allyl dipropyl phosphate and the like.
• the resinous compositions of this invention can be prepared by first effecting the esterification of the selected polycarboxylic acids with the desired polyhydric alcohols in the presence of one of the phosphorus containing materials listed in the next preceding paragraph and in the presence of the reactive unsaturated chemical ingredient, whereby an unsaturated polyester is formed; then mixing the resulting composition with the chosen copolymerizable olefinic cross-linking agent; and, there'- after copolymerizing'the mixture to form an insoluble, infusible polyester resin.
• Another method which may be employed for producing resinous compositions of this invention comprises eifecting the chemical addition of hexahalocyclopentadiene to less than the total theoretical number of olefinic linkages contained in an unsaturated polyester molecule in the presence of one of such phosphorus containing materials listed above.
• a product is produced which contains the hexahalocyclopentadiene in chemical combination in the polyester chain and which also contains active unsaturation which is copolymerizable in the cross-linking reaction; the product so produced is then combined with the chosen olefinic cross-linking agent and thereafter copolymerized.
• Esterification of the desired ingredients may be effected in the presence ofesterification catalysts and/or chain terminating agents, etc.
• a preferred procedure involves introducing the selected ingredients to be esterified, and the phosphorus containing material in predetermined proportions, into a suitable esterification-vessel provided with heating and/or cooling means, an agitator, means for passing an inert gas such as nitrogen or carbon dioxide through the reaction mixture, means for removing water of esterification, an inlet, an outlet, and any other accessories necessary for the reaction.
• the charged reactants are blanketed with an inert atmosphere, then agitated and heated to effect the reaction for the specified period of time.
• the reaction mixture is cooled.
• the resulting product if solid, and if prepared in accordance with the first procedure described, is broken up and then mixed with the olefinic cross-linking agent at room temperature, preferably in the presence of a polymerization inhibitor.
• a hexahalocyclopentadiene is chemically added to a soluble unsaturated polyester molecule in an amount insufficient to react out all the double bonds in the polyester and the material resulting by this treatment is then compounded with the olefinic cross-linking agent.
• cross-linking agent may be advantageously combined with unsaturated polyesters prepared in accordance with these methods while the uni resin.
• a catalyst and/or promoter for the copolymerization may be added, particularly if it is desired to make available in commerce a composition which is ready for polymerization and does not require further chemical additions in order to be used, as is commonly known in the art.
• flame retardance is reported as burning rate in inches per minute determined by ASTM D-757-49, the specifications for this test being:
• a glow bar is heated to 950 degrees centrigrade by alternating or direct current, the electrical input of which is adjusted to 350i20 watts.
• a test specimen 5 x /2' x A; inches is clamped in a holder with its length horizontal and at right angles to the axis of the igniting bar and its width in a vertical plane. The length of the specimen free to burn is four inches. The front end of the specimen is brought into contact With the igniting bar and allowed to remain in this position for three minutes. After three minutes any flaming shall he -extinguished, the specimen removed, and the length burned measured. The length burned divided by three then gave the burning rate in inches per minute.
• Heat distortion temperature defined as that temperature in degrees centigrade a plastic specimen, /a to /2 inch by /2 inch by five inches and supported on its narrowest side by metal supports four inches apart and immersed in a suitable liquid heat transfer medium, which is raised in temperature at a rate of 2 degrees per minute, and under a fiber stress load of 264 pounds per square inch at the center, deflects at the center a distance of 10 mils or 0.01 inch.
• This test is carried out according to ASTM specification D-648-45T titled Heat Dis tortion Temperature of Plastics.
• Color Hazen determined on the liquid polyester resin compound prior to being copolymerized is reported as units of color produced by platinum, in the form of the chloro-platinate ion per liter of water. Each unit of color is that produced by one milligram of platinum,
• EXAMPLE 1 Fifty-two and eight-tenths parts of ethylene glycol and 90 parts of diethylene glycol were charged into an esterification or resin vessel provided with heating and/ or cooling means, an agitator, means for maintaining an atmosphere of an inert gas over the reaction mixture, means for removing water of esterification, temperature recording means, charging inlets and outlets, etc.
• HET 1,4,5,6,7,7-hexachlorobicyclo (2.2.1) 5 heptene 2,3 dicarboxylic anhydride
• the water of esterification liberated during the reaction was separated and periodically measured and the .acid number of the .reaction mixture was also periodically measured to determine the progress of the reaction.
• an acid number of approximately 55 was approached, 3.6 parts .of tetrahydrofurfuryl alcohol was added to the reaction mixture.
• an acid number-of about 45 the entire contents of the reaction vessel was cooled, then cast into pans under an inert atmosphere.
• a transparent, faintly colored, hard, brittle, soluble material, having 38.4 percent by weight chlorine-content, melting in a temperature range above room temperature and below 100 degrees centigrade, and having a specific gravity at room temperature of about i1.45 was obtained.
• EXAMPLE 2 One hundred grams of the cast product recovered in Example 1 was broken into small lumps, then added in small portions, with agitation, to 30 grams of styrene maintained under an inert atmosphere, containing 0.03
• EXAMPLE 3 "Fifty' parts of the mixture prepared in Example 2 were agitated with 0.5 part of a catalyst mixture comprising '50 parts of benzoyl peroxide and 50 parts of tricresyl phosphate. The resulting mixture was cast in a glass tube 16 inches long and having an inside diameter of 1%; inches and set by heating at a temperature of about 80 degrees centigrade for a period of about one-half hour.
• a hard, tough, clear, insoluble, infusible substantially colorless polyester resin was obtained which had a 30 percent chlorine content by weight and which was immediately self-extinguishing on removal from an oxidizing flame, giving a result of 0.18 inch per minute by the .ASTM D-757-49 test, a color Hazen of 120, and a heat distortion temperature of 82 degrees centigrade.
• EXAMPLE 4 One hundred grams of the cast product recovered in Example 1 were broken into small lumps, then added in small portions, with agitation, to 30 grams of diallyl benzene phosphonate, until completely dissolved. The resulting mixture was very viscous.
• EXAMPLE '5 Fifty parts of the mixture prepared in Example 4 were agitated with 0.5 part of a catalyst mixture comprising 50 parts of benzoyl peroxide and 50 parts of tricresyl phosphate. The resulting mixture was cast in a 16 inch by 4 inch inside diameter glass tube and set by heating at a temperature of about 80 degrees centigrade for a period of about one-half hour.
• a hard, clear, insoluble, 'infusible, substantially colorless polyester resin was obtained which had a 30 percent chlorine content by weight ,and which was immediately self-extinguishing on removal from an oxidizing flame, and gave an ASTM D-757-49 acetate p 8 result of 0.12 inch per minute, a color Hazen of and a heat distortion temperature of 82 degrees centigrade.
• the foregoing ingredients were reacted until an acid number of 43.5 was attained, whereupon the contents of the reaction vessel was cooled and then cast under an inert atmosphere.
• the casting was a transparent, substantially colorless, hard, brittle, unsaturated polyester, which when dissolved in 30 percent by weight ofstyrene and copolymerized, employing the benzoyl peroxide catalyst, gave a polyester'resin having a chlorine content of 30 percent, 'a result-of 0.18 inch per minute to theASTM D-757-49 test, a :color Hazen of 165, and a heat distortion temperature of 82 degrees centigrade.
• EXAMPLE 7 Six and two tenths parts of ethylene glycol and 10.6 parts of diethylene glycol were charged in a resin vessel similar to that described .in Example 1 then blanketed with an inert atmosphere, agitated and heated to a temperature of about 100 degrees centigrade, whereupon 38.9 parts of an adduct formed from fumaric acid and hexachlorocyclopentadiene, and 9.8v parts of maleic anhydride were added. The reaction temperature was degrees centigrade, rising to 185 degrees centigrade during the course of 20 hours. At the end of this period a light colored, clear, hard, brittle resin was obtained.
• Example 8 is similar to foregoing Examples 6 and 7 and represents a typical formulation of the polyester resins of this invention without any phosphorous containing compound present and is set forth to indicate a typical fire resistance result obtained from the foregoing described test ASTM D-757-49 in order to contrast this result with those obtained from testing compositions of Examples 9, l0, and 11, which have thesame composition as that of Example 8 except that phosphorus has been chemically combined in the polymerized resin by means of a cross-linking agent.
• EXAMPLE 8 Into a suitable reaction vessel are charged 152 parts of ethylene glycol, 11.6 parts of diethylene glycol, 388.8 parts of HET acid, 152 parts of adipic acid and 59.2 parts of fumaric acid, The esterification was carried out at degrees centigrade under an inert atmosphere of carbon dioxide until an acid number of 17.5 was reached. To 1000 parts of the unsaturated polymerizable resin was added 400 parts of styrene containing 0.14 part of hydroquinone inhibitor. Polymerization was carried out in a manner after Example 3.
• Example 9 There was obtained a clear, hard, resinous materialhav'ing a'22.5 percent chlospanne- EXAMPLES 9, 10, and 11
• Examples 9, and 11 are similar to Example 5 in that phosphorus is introduced chemically into the copolymerized resin by means of a cross-linking agent.
• Table 1 following the examples shows the effect on the burning rate of the materials of these examples as varying amounts of phosphorus are added and also shows that the burning rate may be substantially improved by employing increasing amounts of phosphorus even though the chlorine content of the resin at the same time is decreased.
• compositions of Examples 9, 10, and 11 were made by adding bis (betachloroethyl) vinyl phosphonate in the varying amounts shown in Table I to portions of the styrenated resin of Example 8 but prior to its polymerization.
• To the clear resinous compositions obtained in each case was added 1 percent by weight of a 5050 mixture of benzoyl peroxide and tricresyl phosphate. Polymerization was carried out in a manner after Example 3 resulting in each case in clear, hard, resinous materials.
• Example 8 is repeated in the table as a control.
• Table I -Ph0sph0rus derived from cross-linking agent Polyester Bis (beta Chlorine Burning B esinous ehlcroethyl) Content rate, in./ Ex. No. Cpmposivinyl phosot' final min. as per 7 tion and phonate polymerized ASTM Styrene resin D-757-49 Parts Parts Percent
• Table I reveals that by adding 15 parts of his (betachloroethyl) vinyl phosphonate to 100 parts of the polymerizable compositions of this invention and more particularly of Example 8, the flame resistance was improved more than five fold, i.e. the burning rate became less than one-fifth the rate of the control mate'- rial. Also the improvement in flame resistance was fairly proportional to the amount of the phosphorus containing material added, viz, the more of such material added, the greater the improvement in fire resistance.
• EXAMPLE 12 Into a suitable reaction vessel were charged 91 parts of ethylene glycol, 22.2 parts of diethylene glycol, 388.87 parts of HET acid, and 78.8 parts of fumaric acid. The esterification was carried out at 160 degrees 'centigrade under an inert atmosphere of carbon dioxide untilan acid number of 35 was reached. To 500 parts of the unsaturated polymerizable resin were added 200 parts of styrene containing 0.07 part of hydroquinone inhibitor. Polymerization was carried out in a manner after Example 3.
• Parts Parts Percent I Table II shows the effect on the heat distortion temperature of the final copolymerized resins formed as the maximum amount of di (chloropropyl) propenyl phosphonate which canbe chemically reacted with the polyester portion of the resin is approached and then exceeded. Further discussion of the importance of this data is had in a later portion of this application.
• Examples 17 through 25 typify formulations in which phosphorus is introduced into the final copolymerized resin composition or into the unpolymerized polyester resinous compositions by means of introducing a particular phosphorous containing compound into the esterification reaction vessel with the materials to be esterified. ln Examples 17 and 18 the phosphorus is derived from a material which reacts with the ,acid portion of the polyester. In Example 19 the phosphorus is derived from a material which reacts with both the acid and the alcohol portions of the polyester while in Examples 20 through 25, the phosphorus is derived from a material which reacts with the alcohol portion of the polyester.
• EXAMPLE 18 Into a suitable reaction vessel were charged 427 parts of ethylene glycol, 112 parts of diethylene glycol, 111 parts of bis (hydroxymethane) phosphinic acid, 1955 parts of HET acid and 396 parts of fumaric acid. The esterification was carried out at degrees centigrade under an insert atmosphere of nitrogen until an acid number of 38 was reached. To 1000 parts of the unsaturated polymerizable resin obtained were added 400 parts of styrene containing 0.14 part of hydroquinone inhibitor. Polymerization was carried out in a manner after Example 3 openneand a clear, hard, resinous material having the properties set forth in Table III was obtained.
• EXAMPLE 19 Three hundred and sixty four parts of ethylene glycol, 89 parts of diethylene glycol, 41.5 parts of hydroxymethyl phosphonic acid, 314 parts of fumaricacid, and 1550 parts of HET acid were charged into a suitable reaction vessel.
• the reactants were esterified under an inert atmosphere of'nitrogen and at an elevated temperature of 160 degrees centigrade until an acid number of 33.4 was reached.
• To 1000 parts of the polymerizable unsaturated polyester obtained were added 400 parts of styrene containing 0.14 part of hydroquinone inhibitor. Polymerization was carried out in a manner after Example 3 and a clear, hard, resinous material having the properties set forth in Table III was obtained.
• EXAMPLE 20 Nine hundred forty three and three tenths parts of ethylene glycol, 230.8 parts of diethylene glycol, 34 parts of phosphorous acid, 766.6 parts of fumaric acid and 4025.6 parts of HET acid were charged into a suitable reaction vessel. The reactants were esterified under an inert atmosphere of nitrogen and at an elevated temperature of 160 degrees centigrade until an acid number of 33.5 was obtained. To 5000 parts of the polymerizable unsaturated polyester obtained were added 2000 parts of styrene containing 0.70 part of hydroquinone inhibitor. Polymerization was carried out in a manner after Example 3 and a clear, hard, resinous material having the properties set forth in Table III was obtained.
• EXAMPLE 21 Nine hundred forty three and twenty seven one hundredths parts of ethylene glycol, 230.75 parts of diethylene gylcol, 56.87 parts of phosphorus trichloride, 766.57 parts furamic acid and 4025.58 parts of HET acid were charged into a suitable reaction vessel. The reactants were esterified under an inert atmosphere of nitrogen and at an ele- .vated temperature of 160 degrees centigrade until an acid number of 32.3 was obtained. To 5000 parts of the polymerizable unsaturated polyester obtained were added 2000 parts of styrene containing 0.70 gram of a hydroquinone inhibitor. Polymerization was carried out in a manner after Example 3 and a clear, hard, resinous material having the properties set forth in Table III was obtained.
• EXAMPLE 22 To a suitable reaction vessel were charged 236 parts of ethylene glycol, 58 parts of diethylene glycol, 11.2 parts of phosphoric acid (85% 1006 parts of HET acid and 192 parts of fumaric acid. The esterification was carried out at an elevated temperature of 160 degrees centigrade under an inert atmosphere of nitrogen until an acid number of 34 was reached. To 1000 parts of the unsaturated polymerizable resin were added 400 parts of styrene containing 0.14 part of hydroquinone inhibitor. Polymerization was carried out in a manner after Example 3 and a 'clear, hard, resinous material having the properties set forth in Table III was obtained.
• EXAMPLE 23 Nine hundred fifty nine and four tenths of ethylene .glycol, 234.5 parts of diethylene glycol, 756 parts of .fumaric acid, 198.3 parts of benzenephosphonic acid and 3.85.1.8 parts of HET acid were charged into a suitable reaction vessel. The reactants were esterified under an .inert atmosphere of nitrogen and at an elevated tempera- ;ture of 160 degrees centigrade until an acid number of 28.2 was obtained.
• EXAMPLE 24 Ninety one parts of ethylene glycol, 23 parts of diethylene glycol, 74 parts of fumaric acid, 47 parts of phosphorus oxychloride and 389 parts of HET acid were charged into a suitable reaction vessel. The reactants were esterified under an inert atmosphere of nitrogen and at an elevated temperature of 160 degrees centigrade until an acid number of 36.1 was obtained. To parts .Of the polymerizable unsaturated polyester were added 40 parts of styrene containing 0.014 part of hydroquinone inhibitor. Polymerization was carried out in a manner after Example 3 and a clear, hard, resinous material having the properties set forth in Table III was obtained.
• EXAMPLE 25 Ninety one parts of ethylene glycol, 23 parts of diethyb ene glycol, 74 parts of fumaric acid,64.5 parts of phosphorous pentachloride and 389 parts of HET acid were charged into a suitable reaction vessel. The reactants were esterified under an inert atmosphere of nitrogen and at an elevated temperature of degrees centigrade until an acid number of 35.5 was obtained. To 100 parts of the polymerizable unsaturated polyester were added 40 parts of styrene containing .014 part of hydroquinone inhibitor. Polymerization was carried out in a manner after Example 3 and a clear, hard, resinous material having the properties set forth in Table III was obtained.
• phosphme oxide 18 Bis-hydroxy- 39.3 28 1.0 0 72 methane phosphinic acid. 19. Hydroxymethyl 45.8 32. 7 0. 54 0.39 0. 10
• the table shows that as styrene is added, prior to EXAMPLE 39 polymerization, the viscosity is reduced almost 20 times without incurring a loss in fire resistance. This is important because for many commercial processes, low viscosity resinous compositions are necessary.
• the table also shows that even though the chlorine content of the final copolymerized resins is lowered by the increasing amounts of styrene added, the flame resistance of the resins is not adversely afiected. In contrast to this, the same type resin A, without any phosphorus incorporated therein gives burning rates of 0.19, 0.21, 0.22, and 0.23 in Examples 26, 27, 28, and 29 respectively.
• polyester resinous compositions set forth in Table V are similar to those previously described and are also capable of having their flame resistant properties improved by the addition of phosphorous by means of any of the phosphorus containing materials previously mentioned:
• Adduct of hexahalocyclopentadiene and fumaric acid 28. 9 Cast material of Example 4...- 24. 2 31 +diallyl 1,4,5,6,7,7-hexachlorobicyclo-(2.2.1)-5-heptene-2,3-dicarboxylate (Ad- 9. 7
• dride (Adduct of liexahaloeyclopentadiene and Citraconic anhydride). 33 16.6 28. 4 26. 4 mono-methyl ester of 1,4,5,6,7,7-hexachlorobicyclo-(2.2.1)-5-heptene-2,3-dicar- 114. 4
• boxylic acid (Adduct of hexahalocyclopentadiene and maleic anhydride, half esterified with methanol). 34 24. 5 3-(1,4,5,6,7;7-hexachlorobieyclo(2.2.1)-5-heptene-2-yl)-methoxy-1,2-propanediol 101. 3
• halocyclopentadienes and 2-butene-1,4-dio1 1 38 13. 2 22. 4 17. 4 1,4,5,6,7,7hexachloro-2-chloro-bicyclo-(2.2.l)- -heptene-2,3-dicarboxylic anhy- 110 dride (Adduct oi hexahalocyclopentadiene and chloro maleic anhydride).
• Examples 39 through 44 are given in order to establish that when proceeding in accordance with our invention the phosphorus becomes chemically combined in the polymerized resin.
• Examples 39, 40, 41, and 42 show that when triethyl phosphate, tricresyl phosphate, triphenyl phosphate or tributyl phosphate are incorporated in the polyester resin by the procedures depicted that these are not chemically combined into the final polymerized resin but merely are physically combined in the resinous composition as additives because in each case the heat distortion temperatures of the finally polymerized resins formed are adversely affected.
• a resin was made by reacting 633.1 parts of HET acid, 128.1 parts of fumaric acid, 148.3 parts ethylene glycol and 36.2 parts diethylene glycol. These materials were charged into a 1 liter reaction vessel provided with a nitrogen inlet, a stirrer, a thermometer and means for distillation of water of esterification. The reaction was carried out at degrees centigrade with stirring and nitrogen passing through the mix. When an acid number of 34 had been reached the resin was poured out into a tray and allowed to cool. To 100 parts of this resin was added 40 parts of styrene and the mixture was brought to complete solution. To 100 parts of this styrenated,
• tricresyl phosphate was then added parts of tricresyl phosphate.
• This mixture was catalyzed by adding 2 parts of Luperco ATC, a mixture of 50 parts of tricresyl phosphate and 50 parts of benzoyl peroxide.
• the catalyzed resin was pouredinto a tube and cured at 50 degrees centigrade in a water bath a for 24 hours followed by 24 hours curing at 120 degrees centigrade. The heat distortion was then determined and it was found to be 83 degrees centigrade.
• EXAMPLE 41 The styrenated resin composition of Example 40 was also used in this example, 41. To 100 parts of this styrenated resinous composition was added 10 parts of triphenyl phosphate. The catalyzation and curing of this resin were carried out in the samemanner as Example 40. In this case the heat distortion temperature was found to be .83 degrees centigrade. Triphenyl phosphate, and tricresyl phosphate are well known in the art as being flame proofing additives for resins and plastics. It also is well known that they exhibit a plasticizing action and that they lower the heat distortion temperature of the rigid thermoset products to which they are added.
• EXAMPLE 42 Eight hundred three and four tenths grams of HET acid, 162.6 grams of fumaric acid, 1.69.6 grams of ethylene glycol, 46.0 grams ofdiethylene glycol and 39.9.grams of tributyl phosphate were charged into a 1 liter reaction vessel provided with means for introduction of nitrogen to the bottom of the reaction mix, a stirrer, thermometer and an outlet for distillation of water of esterification. The reaction vessel was heated with stirring and passage of nitrogen at a temperature of 160 degrees centigrade until an acid number of 43 had been reached. The contents were then cast out into trays. One hundred parts of this base resin were dissolved in 40 parts of styrene. The water of esterification of this reaction was analyzed for butyl alcohol.
• EXAMPLE 43 A resin was made using the following proportion of materials: HET acid 633.1 parts, fumaric acid 128.1 parts,
• EXAMPLE 44 A resin was made using the following properties of materials: HET acid 633.1 parts, fumaric acid 128.1 parts, ethylene glycol 148.3 parts, and diethylene glycol 36.2 parts. The mixture was charged into a 1 liter reaction vessel provided with nitrogen inlet leading to the bottom of the flask, stirrer, thermometer and means for water of esterification distillation. The flask was heated at a temperature of 160 degrees centigrade until an acid number of 34 had been reached. The mixture was then poured out into trays and allowed to cool. One hundred parts of this base resin was dissolved in 40 parts of styrene.
• the heat distortion temperature results show an improvement over resins without any phosphorus incorporated therein or at least are approximately as good as resins with out any phosphorus incorporated therein, while in that example where the limit of phosphorus in chemical combination has been exceeded, the di(chloropropyl propenylphosphonate) then functions as a plasticizer and the heat distortion temperature result falls off badly.
• the temperature for carrying out the reaction between the polyhydric alcohols and polybasic acids ranges from 100 degrees centigrade and to 200 degrees centigrade, although higher or lower temperatures can be used; preferably around degrees centigrade to degrees centigrade is advantageously employed.
• An inert gas such as nitrogen is passed through the mixture in a preferred procedure to accelerate the progress .of the reaction and allow for good color of the product.
• the progress of the reaction is followed by measuring .the rate of water liberated, by the viscosity of the resin, by its acid number, or by other methods commonly known in the art.
• the extent to which the reaction is carried out will depend on a number of factors, such as the desired viscosity, melting point, duration of reaction, etc.
• Esterification catalysts such as para-toluene sulfonic acid, benzene sulfonic acid, beta naphthalene sulfonic acid, etc., or amines such as, pyridine, triethyl amine, quinoline, etc., may be added to the reaction mixture.
• the proportion of polyhydric alcohol is approximately controlled by the total mol proportion of acids in the percent.
• a chain stopper may be added in a minor proportion depending on the molecular weight of the linear unsaturated polyester chain desired, in-order to ra'pidly termivnate the growth of the unsaturated polyester chain during the esterification reaction and when the desired acid number is being approached, or, to reduce the number of free carboxyl or hydroxyl groups, or, to introduce a hydrocarbon terminal residue.
• the compounds which may be used as chain stoppers during the esterifiis produced are a wide variety of monohydric alcohols,
• the solution or mixture-of unsaturated polyester and olefinic cross-linking agent is preferably made While'the unsaturated polyester is still hot, thereby facilitating rapid solution.
• the unsaturated polyester may be cooled and stored and whenready for mixing may be heated in order to facilitate solution in the olefin, which may also be heated.
• the solution may, of course, be made in the cold, especially if there is any possibility of explosion in handling the hot olefinic cross-linking agent ,or if polymerization of the olefinic cross-linking agent.
• the proportion of olefinic cross-linking agent to unsaturated polyester may be varied within the ultimate limits of each without departing from the scope of this .invention, in order to make the solution or mixture of this invention which may be set to the infusible, insoluble, polyester resin.
• olefinic cross-linking .agent is needed when the proportion of reactive cross-linkable olefinic bonds in the unsaturated polyester is very small; and a still srnaller proportion of olefinic cross-linking agent may be employed if it is desired to react only a part of the totalof said unsaturated bonds in such polyester in the crosslinking reaction.
• a major proportion '15 cation reaction whereby the unsaturated polyester chain moters such as metals or metal salts; cobalt maleate,
• cobalt naphthenate etc.
• amines such as dibutyl amines, or mercaptans such as dodecyl mercaptan, etc.
• mercaptans such as dodecyl mercaptan
• the polymerization conditions for effecting the cross- *linking reaction between the unsaturated polyesters of this invention and the olefinic cross-linking agent may be selected from a wide variety of techniques but usually involve theapplication of heat or light; Although pressure is not a required condition for effecting polymerization of the polymerizable mixtures embraced within this invention, thereby providing a decided advantage over other insoluble, infusible resins known heretofore, it is sometimes advantageously employed, particularly when it is desired to make laminates in preformed shape.
• pressures found satisfactory for this purpose are'relative'ly low compared to those required for molding or laminating other type resins than involved herein and may be of the order of that obtained by pressing glass plates having a fiber glass mat or laminate impregnated With the polyester resin sandwiched therebetween.
• the temperature at which polymerization is effected depends on a variety of factors, particularly the boiling point of the olefinic cross-linking agent and the exothermic characteristics of the polymerization mixture.
• olefinic cross-linking agent to unsaturated polyester may be employed when the proportion of reactiveicross linkable olefinic bonds in the unsaturated polyester is high; and a still higher proportion of olefinic cross-link- .ing agent will be required if ittis desired to react a major part of the total of said unsaturated bonds in such polyester in the cross-linking reaction.
• concentration of the unsaturated polyester in the olefinic cross-linking agent may vary between about 10 and 90 centuate a large number of desirable properties in the ever, it is to be understood that this preferred concentration is a variable which is dictated by the particular properties of the materials employed and the particular I properties desired in the polyester resin produced.
• Polymerization inhibitors usually of the order of 0.001 to 1 percent of the composition may be added to prevent premature polymerization.
• the inhibitors which may advantageously be employed to prevent the premature polymerization of the mixture of unsaturated polyester and olefinic cross-linking'agents, particularly if the mixture is to be stored or shipped in commerce prior to curing, are substances such a hydroquinone, benzoquinone, para-tertiary-butyl catechol, paraphenylene diamine, trinitrobenzene, picric acid, etc.
• hexahalocyclopentadienes may be employed in making compositions embraced within the scope of this invention such as the chloro, bromo and fiuoro substituted .cyclopentadienes wherein all of the hydrogens are replaced by one or more of the foregoing halogens. While hexachlorocyclopentadiene is today the most readily available hexahalocyclopentadiene, we have found that the mixed perhalo compounds are useful in making Diels- Alder-adducts which can be chemically combined into the saturated polyester compositions of this invention.
• hexachlorocyclopentadiene in which one or two of the chlorine atoms has been replaced with bromine, appears to afford an even higher degree of flame retardance in the polyester resins.
• the compounds useful in making adducts of hexahalocyclopentadienes are dienophiles having a plurality of esterifiablegroups. These functional groups capable of estcrification and having utility herein are found in compounds such as substituted or unsubstituted acids, anhydrides, acid halides, alcohols and esters, as hereinbefore illustrated.
• the hexahalocyclopentadiene radical may be combined into the polycarboxylic acid unit of the unsaturated polyester chain in a variety of ways such as by effecting the Diels-Alder reaction of the hexahalocyclopentadiene with unsaturated polycarboxylic acids such as maleic or in 19 maria; substituted maleics or fumarics such as, citraconic, chloromaleic, mesaconic, and pyrocinchonic; acetylene dicarboxylic acids; and also ethylenic substituted succinic anhydrides or acids, such as, aconitic and itacouic, etc.
• unsaturated polycarboxylic acids such as maleic or in 19 maria
• substituted maleics or fumarics such as, citraconic, chloromaleic, mesaconic, and pyrocinchonic
• acetylene dicarboxylic acids and also ethylenic substituted succinic an
• adducts of hexahalocyclopentadiene with substances which produce an equivalent polyester chain upon reaction with a polyhydric alcohol can be used; for instance, acid chlorides, or, esters of the acids or anhydrides mayalso be used.
• acid chlorides or, esters of the acids or anhydrides may also be used.
• a typical illustration is had in the Diels-Alder reaction of hexachlorocyclopentadiene with fumaryl chloride to produce l,4,5,6,7,7-hexachlorobicyclo-(2.2.1)--heptene-2,3 dicarbonyl chloride followed by the esterification of this with ethylene glycol and maleic anhydride to produce the unsaturated polyester.
• diesters such as, dimethyl maleate may be employed.
• the hexahalocyclopentadiene radical may be combined into the polyhydric alcohol unit of the unsaturated polyester chain in a variety of ways such as, by effecting the Diels-Alder reaction of the hexahalocyclopentadiene with unsaturated polyhydric alcohols such as, butene-diol or pentene-diol, etc.
• Other suitable compounds are ethers or esters derived from polyhydric alcohols having at least three hydroxyl groups, one of which is esterified or etherified with an unsaturated alcohol or acid reactive with hexahalocyclopentadiene in the diene synthesis.
• allyl or vinyl glycerol ethers for instance, allyl or vinyl pentaerythritol ethers; and unsaturated acid esters of glycerol or pentaerythritol, etc., such as, acrylic or methacrylic esters thereof may be used.
• unsaturated acid esters of glycerol or pentaerythritol, etc. such as, acrylic or methacrylic esters thereof
• a polyhydric alcohol in the Diels-Alder reaction
• adducts of hexahalocyclopentadienes with substances which produce an equivalent unsaturated polyester chain, upon reaction with a polycarboxylic acid can be used; for instance, esters of the alcohols may also be used.
• the unsaturated polyester chains produced by effecting the Diels-Alder reaction of hexahalocyclopentadiene with an unsaturated polycarboxylic acid or polyhydric alcohol, followed by the esterification of the product so pro- ,duced with a polyfunctional alcohol or acid, can be rendered copolymerizable by chemically combining in such polyester chains, a reactive and unsaturated chemical ingredient which retains its active unsaturation after its chemical combination into the polyester chain.
• the unsaturated polycarboxylic acids such as, maleic, fumaric, citraconic, itaconic, acetylene dicarboxylic and esters and halogen substituted derivatives thereof, etc.
• the unsaturated polyhydric alcohols such as, butene-diol, pentene-diol, etc., also unsaturated hydroxy ethers such as allyl or vinyl glycerol ethers, allyl or vinyl pentaerythritol ethers, etc.
• still other chemical compounds comprising an ethylenic or an acetylenic linkage which are not rendered unreactive in the polyester chain by their chemical combination into the polyester chain by way of other functional groups, whereby the mixed esters are produced.
• Another method of providing for copolymerizable unsaturation in the polyester chain involves: effecting the diene synthesis of hexachlorocyclopentadiene with a polybasic alcohol or acid or ester, or equivalents thereof, which contains at least two olefinic linkages, one of which is reactive in the diene synthesis, while the others which are unreacted, are capable of being copolymerizable in the cross-linking reaction.
• the materials which are useful for this purpose are acetylenic compounds and di-olefinic and poly-olefinic compounds.
• the chlorine content of the final polyester formulations may be obtained, or substantiallyincreased, by employing a cross-linking agent which also contains the component which imparts flame retardance to the final compositions of this invention.
• cross-linking agents which may be useful for this purpose are the following: diallyl-1,4,5,6,7,7-hexachlorobicycle-(2.2.1)-5-heptene-2,3-dicarboxylate; diallyl-1,4,5,6, 7,7 hexachloro- 2 methylbicyclo (2.2.1) 5 heptene-2,3-dicarboxylate; diallyl-l,2,4,5,6,7,7-heptachl0robicycle-(2.2.1)-5-heptene-2,3-dicarboxylate; and triallyl- 1,4,5,6,7,7 hexachlorobicyclo (2.2.1) 5 heptene 2- acetate-2,3-dicarboxylate.
• These compounds can be prepared by reacting hexachlorocyclopentadiene with the indicated dicarboxylic acid and esterifying the resultant product with an unsaturated alcohol such as allyl alcohol.
• cross-linking agents may advantageously be employed; for example, reaction products of hexachlorocyclopentadiene with isoprene or butadiene retaining a reactive unsaturated linkage can be used as cross-linking agents directly without further reaction. Still other methods for the preparation of the unsaturated crosslinking agents, employing type reactions known to the art, will be apparent from the foregoing.
• materials such as triallyl cyanurate may be employed for improving heat resistance; divinyl benzene, monochlorostyrene, dichlorostyrene, diallyl phthalate, diallyl maleate and similar monoor poly-vinyl or monoor poly-allyl derivatives are also useful.
• the hexachlorocyclopentadiene content should not comprise less than'seven percent by weight of the polyester resin compositions; the upper limit for the hexachlorocyclopentadi. ene content is generally dictated by practical limits determined by the minimum necessary .concentration of glycols and unsaturated dibasic acids not being adducts of hexachlorocyclopentadiene and olefins to give resinous compounds capable of being hardened and this upper limit is about 60 percent.
• Flame retardance may be accentuated by adding to the unsaturated polyester containing the hexachlorocyclopentadiene component, a cross-linking agent which also contains the flame retardant component made from hexachlorocyclopentadiene in chemical combination therewith. It may be further accentuated by esterifying a polycarboxylic acid and polyhydric alcohol which each contain the hexahalocyclopentadiene flame retardant component of this invention and cross-linking this with a fire resistant crosslinking agent. It may be even further accentuated by chemically incorporating phosphorus in the ways previously described in this application.
• compositions of this invention can be varied substantially by incorporating modifying agents before, during or after any of the processing steps employed.
• a foamed type article may be made by incorporating a small percentage of a foaming agent such as sodium bicarbonate into the solution of unsaturated polyester dissolved in mono-olefin and thereafter effecting the copolymerization in the presence of catalyst and heat to produce the foamed article.
• Formulations which are useful for making moldings embodying the compositions of'this invention may be made by mixing into the unsaturated linear polyester and olefinic cross-linking agent mixture, an inert filler such as chopped fiber glass rivings, macerated fabric, asbestos fibers, mica, etc., which serve as fibrous reinforcing media and incorporating a small percentage of a mold lubricant,'catalyst and-or promoter,
• An infinite variety of products may also be prepared, which embody the compositions of this invention, by copolymerizing the linear unsaturated polyester materials produced inaccordance with this invention, as in Example 1, with a mono-olefinic cross-linking agent in the presence of another copolymerizable linear polyester material having different structure than that produced by this inveution.
• a polymerizable mixture comprising (A) a polymerizable linear polyester resin, comprised of "the reaction product of a polycarboxylic acid and a polyhydric alcohol, said resin having olefinic copolymerizable unsaturation and (B) a vinylidene monomer; an ingredient (l) of said mixture containing a chemically combined component which is a chemical reaction adduct of hexahalocyclopentadiene wherein the halogen is selected from the group consisting of chlorine, bromine, fluorine, and mixtures thereof, with a material selected from the group consisting of a polycarboxylic compound containing aliphatic carbon to carbon unsaturation and a polyhydric alcohol containing aliphatic carbon to carbon unsaturation, wherein said polycarboxylic compound is selected from the group consisting of polycarboxylic acids, polycarboxylic anhydrides and polycarboxylic acid halides, and an ingredient (II) of said mixture containing a compound of
• a reinforced plastic article comprising a composition of claim 1 when polymerized to an infusible, insoluble, resinous composition, and a fibrous reinforcing medium.
• a laminated article comprising a plurality of sheets of glass fibrous material and as a binder therefor, an infusible, insoluble, resinous composition resulting from the polymerization of a composition defined in claim 1.
• a composition of claim 10 wherein said adduct is the chemical reaction adduct of hexahalocyclopentadiene and a polycarboxylic compound containing aliphatic carbon to carbon unsaturation selected from the group consisting of polycarboxylic acids, polycarboxylic anhydrides and polycarboxylic acid halides wherein the halogen is selected from the group consisting of chlorine, bromin fluorine, and mixtures thereof.
• a composition of claim 11 wherein said adduct is the chemical reaction adduct of hexahalocyclopentadiene and a polyhydric alcohol containing aliphatic carbon to carbon unsaturation wherein the halogen is selected from the group consisting of chlorine, bromine, fluorine, and mixtures thereof.
• a composition of matter comprising a polymerizable linear polyester resin, comprised of the reaction product of a polycarboxylic acid and a polyhydric alcohol, said resin having olefinic copolymerizable unsaturation; an ingredient (I) of said composition containing a chemically combined component which is a chemical reaction adduct of hexahalocyclopentadiene wherein the halogen is selected from the group consisting of chlorine, bromine, fluorine, and mixtures thereof, with a material selected from the group consisting of a polycarboxylic compound containing aliphatic carbon to carbon unsaturation and a polyhydric alcohol containing aliphatic carbon to carbon unsaturation, wherein said polycarboxylic compound is selected from the group consisting of polycarboxylic acids, polycarboxylic anhydrides and polycarboxylic acid halides, and an ingredient (II) of said mixture containing a compound of phosphorus, both the adduct of (I) and the phosphorus of
• a composition of claim 14 wherein the hexahalocyclopentadiene is hexachlorocyclopentadiene.
• a composition of claim 14 when mixed with an inert filler 16.
• a composition of claim 14 wherein said adduct is the chemical reaction adduct of hexahalocyclopentadiene and a polycarboxylic compound containing aliphatic carbon to carbon unsaturation selected from the group consisting of polycarboxylic acids, polycarboxylic anhydrides and polycarboxylic acid halides wherein the halogen is selected from the group consisting of chlorine, bromine, fluorine, and mixtures thereof.
• composition of claim 14 wherein said adduct is the chemical reaction adduct of hexahalocyclopentadiene and a polyhdric alcohol containing aliphatic carbon to carbon unsaturation wherein the halogen is selected from the group consisting of chlorine, bromine, fluorine, and mixtures thereof.

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